TWI238833B - Catalysts and method for polymerization of olefins - Google Patents

Abstract

A catalyst for the polymerisation of 1-olefins is disclosed comprising (1) a compound of the formula B, wherein M is Fe[II], Fe[III], Co[I], Co[II], Co[III], Mn[I], Mn[II], Mn[III], Mn[IV], Ru[II], Ru[III] or Ru[IV]; X represents an atom or group covalently or ionically bonded to the transition metal M; T is the oxidation state of the transition metal M and b is the valency of the atom or group X; R1, R2, R3, R4, R5, R6 and R7 are independently selected from hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R1-R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, said two or more can be linked to form one or more cyclic substituents; (2) an activator which is an alkylalumoxane; and (3) additionally to (2), a compound of the formula AlR3, where each R is independently C1-C12 alkyl or halo. Preferred compounds (3) include trimethylaluminium (TMA) and triisobutylaluminium (TIBA).

Description

1238833 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 V. Description of the invention (1) Description of the invention The present invention relates to transition metal compounds and polymerization catalyst systems using the transition metal compounds. The use of certain transition metal compounds to polymerize olefins such as ethylene has been well established in the prior art. The use of Ziegler-Natta catalysts', for example, catalysts made by activating titanium dentates with organometallic compounds such as triethylaluminum, are the basis of many commercial polyolefin manufacturing methods. Advances in the technology over the past two to three decades have led to the development of Ziegler-Natta catalysts with relatively high activity. Therefore, it is possible to directly produce dilute smoked polymers and copolymers with extremely low concentrations of residual catalysts in commercial polymerization processes. The amount of residual catalyst remaining in the resulting polymer is so small that it does not need to be separated or removed for most commercial applications. This method can be operated by polymerizing monomers in the gas phase or in a liquid hydrocarbon diluent solution or suspension. Polymerization of monomers can be performed in the gas phase ("gas phase method"), for example, using a fluidized gas stream containing gaseous monomers under polymerization conditions; ILization of a bed containing the target polyhydrocarbon powder and predetermined catalyst particles. In the "solution method", the (co) polymerization reaction is performed through the production of polyolefins to form a solution or suspension of a hydrocarbon diluent at a temperature and pressure of a solution of a hydrocarbon diluent, by introducing a monomer into a liquid hydrocarbon diluent. . In the "liquid-filling method", the temperature, pressure, and diluent are selected so that the resulting polymer forms a suspension with the liquid hydrocarbon diluent. These methods are usually carried out at relatively low pressures (e.g. 10 to 10 bar) and low temperatures (e.g. 50 to 150 ° C). Commodity products are commercially produced in many different types and grades. Homopolymerization of ethylene with a base and a transition metal-based catalyst results in the production of so-called "high density" polyethylene. These polymers have a relatively high paper size. Applicable to China National Standard (CNS) A4 specifications (210X297 mm) (Please read the precautions on the back before filling this page)

If 1238833

Printed by the Consumer Cooperatives of the Central Sample Bureau of the Ministry of Economic Affairs

Stiffness can be used for objects that require rigid properties. Ethylene is copolymerized with higher carbon olefins (such as butene, hexene, or heptene) to provide a variety of copolymers, which differ in density and other major physical properties. Particularly important copolymers made via the copolymerization of ethylene with high-carbon 1-olefins using a transition metal-based catalyst are copolymers having a density in the range of 0.91 to 0.93. These copolymer industries are often referred to as "linear low-density polyethylene" and are similar in many respects to the so-called "low-density polyethylene" produced by the high-pressure free-radical catalytic polymerization of ethylene. These polymers and copolymers are widely used in the manufacture of flexible blown films. One of the major features of the microstructure of the copolymer of ethylene and high-carbon 1-olefins is that the comonomer units after polymerization are distributed along the "backbone" chain of the ethylene units after polymerization. The conventional Ziegler-Natta catalysts tend to produce copolymers in which a total of 1 monomer units are polymerized along the chain after polymerization. In order to achieve particularly desirable film properties from such copolymers, it is preferred that the comonomer units within each copolymer molecule do not clump together, but instead are completely spaced along the length of each linear polyethylene chain. In recent years, the use of certain metallocene catalysts (such as aluminoxane-fluorenated cyclopentadienyl dichloride) has provided catalysts with high activity and can provide improved comonomer unit distribution. . However, this type of metallocene catalyst has various disadvantages, such as the high sensitivity to impurities when using commercially available monomers, diluents, and process gas streams, and the use of a large number of expensive alumoxanes to achieve high activity, and the proper placement of the catalyst Difficulty alone. W098 / 27124 discloses that ethylene is polymerized by contact with certain selected 2,6_heridine carboxal hydrazones (imines) and 2,6-diamidino uridine (imines) iron or cobalt complexes. These complexes are revealed to be suitable for preparing ethylene homopolymers. It is shown to have an activity of 6 to 2985 g / mole / hour / bar. (Please read the notes on the back before filling this page) Order -I-—--I-

The standard of this paper is the standard of housekeeping (cns) Α4 · (2.iGx297mm)--I--· 1238833 A7 B7 V. Description of the invention (3) The inventor has developed and used the mismatch disclosed in, for example, WO 98/27124 Novel catalysts that can provide excellent activity and products. As such, in the first aspect, the present invention provides a catalyst for polymerizing olefins comprising (1) a compound of formula B

(Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs where M is Fe [II], Fe [III], Co [I], Co [II], Co [III] , Mn [I], Mn [II], Mn [III], Mn [IV], Ru [II], Ru [III] or Ru [IV]; X means covalent or ionic bonding to the transition metal M Atom or group; T is the oxidation state of transition metal M, and b is the valence of X atom or group; R1, R2, R3, R4 'R5, R6 and R7 are each selected from hydrogen, halogen atom, hydrocarbon group, substituted hydrocarbon group , Heteroalkyl or substituted heteroalkyl; and when any two or more of R ^ R7 are hydrocarbon, substituted hydrocarbon, heteroalkyl or substituted heteroalkyl, these two or more may be bonded to form one or more rings (2) an activator which is an alkyl radical; and (3) a compound of the formula A1R3, in addition to (2), where each R is a C, C12 alkyl or _ atom. Invention It has been found that a significant improvement in the activity can be obtained by mixing the component (3) to the catalyst. The three substituents R of the compound (3) may be the same or different, and is preferably hydrogen, fluorenyl, ethyl, butyl or gas. The preferred compound (3) includes trimethylaluminum ( (TMA) The paper size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 1238833 A7 B7 V. Description of the invention (4), triethylaluminum (TEA), three Isobutylaluminum (TIBA), tri-n-octylaluminum, ethylaluminum dichloride and gasified diethylaluminum. The best are TMA and TIBA. But the preferred compound (3) depends on the polymerization conditions of the catalyst used. Decision: For example, TMA can particularly effectively improve the activity of the catalyst in the gas phase, and it can also improve the activity of the unsupported catalyst in the slurry phase, and TIB A is generally particularly effective for the slurry phase. As for the activator ( 2) The catalyst of the present invention includes an alkylalumoxane, which is usually (Ci-CJ alkylalumoxane, and the alkyl group is usually methyl, ethyl, propyl or isobutyl. Preferred is methyl Alumoxane (also known as fluorenyl alumoxane or MAO) or modified methylalumoxane (MMAO), which additionally contains isobutylalumoxane. The term "alkylalumoxane" used in this specification Including commercially available alkylaluminoxanes containing about 10 wt%, but with selectivity up to 50 wt%, corresponding to trialkylaluminum; For example, the commercially available MAO generally contains about 10 wt% trimethylaluminum (TMA), and the commercially available MMAO contains TMA and TIBA. The oxygen content of the burned bases referred to here includes the impurities of the burned bases. Ingredient (3) is considered to be a compound of formula A1R3 other than any A1R3 compound mixed with alkylaluminoxane (2), and the amount of ingredient (3) cited herein is also calculated on this basis. In the catalyst system, the amount of the activated compound (2) to be used is usually determined through simple tests, such as preparing a small test sample, which can be used to polymerize a small amount of monomers, thus determining the catalyst activity generated. It is generally found that this amount is sufficient to provide 0 "to 20,000 atoms, preferably 1 to 2,000 atoms of aluminum, for each Fe, Co, Mn or Ru metal atom in the compound of formula B. The amount of the activator (2) required for optimal performance is also determined by the amount of the aluminum alkyl compound (3). For example, when the compound (3) is trimethylaluminum (TMA), and the paper size applies to the Chinese National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page)

1T #f 1238833 Δ7 Α7 Β7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (5) When the amount of TMA in the medium is less than 500 mol equivalents of the metal atom of compound (1), the alkyl aluminum oxide The amount of alkane (usually MAO) is preferably at least 1,000 mole equivalents. However, if 500,000 equivalents or more of TAM is present, the optimum amount of alkylaluminoxane (usually MAO) is 500 to 1000 equivalents. Preferably, in the above formula B, M is Fe [II], Fe [III], Ru [n], Ru [III] or Ru [IV]; X represents an atom covalently or ionicly bonded to the transition metal M Or T; T is the oxidation state of transition metal M, and b is the valence of X atom or group; R1, R2, R3, R4, R5, R6, and R7 are selected from hydrogen, halogen atom, hydrocarbon group, substituted hydrocarbon group, hetero Hydrocarbyl or substituted heterohydrocarbyl; and when any two or more of R ^ R7 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, these two or more may be bonded to form one or more cyclic substitutions base. Other compounds useful in the present invention include those comprising a backbone unit of formula Z

Where M is Fe [II], Fe [III], Co [I], Co [II], Co [III], Mn [I], Mn [II], Mn [III], Mn [IV], Ru [ II], Ru [III] or Ru [IV]; X represents an atom or group covalently or ionicly bonded to the transition metal M; T is the oxidation state of the transition metal M, and b is the valence of the X atom or group; R1 to R4, R6 This paper size is applicable to Chinese National Standard (CNS) A4 specification (21 × 297 mm) (read the precautions on the back before filling this page), 1T #f 1238833 5. Description of the invention (6 and R : m is not selected from the group consisting of hydrogen, atom, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl, when any one or more of R1j_R4, r6 & r19 to r28 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterocarbyl Hydrocarbyl group = equal-or more can be linked to form-or more cyclic substituents; stipulated that when neither of the ring systems P and Q constitute a part of the polyaromatic slightly ring system, R19 r °, R21 And at least one of R22 is a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, or a substituted heterohydrocarbyl group. This particular aspect of the present invention is preferred when any of the ring systems does not form part of a polyaromatic ring system. Medium Page = less-person mR22 At least one of them is selected from the group consisting of hydrocarbyl-substituted nicotine, heterohydrocarbyl, or substituted heterohydrocarbyl; and most preferably R1 ?, R2G, ^^, and ^ 22 are each selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heteronicotyl. · The Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs printed the provisions of R19, R20, R21, and R22 of the formula Z above. R1R4'aRi9 to R28 in the compounds shown by ^ and Z of the present invention are preferably selected from lice and ㈣Hydrocarbyl, such as methyl, ethyl, n-propyl, n-butyl, bis: octyl: the formula "'ca is preferably selected from substituted or unsubstituted square, hetero-5 or aromatic groups, such as Phenyl '1-naphthyl' 2-Cetolyl 2-fluorenylphenyl, 2-ethylphenyl, 26_diisopropylphenyl, π: methyl ^ phenyl, 2,4 · diisopropyl Phenyl, ¥ di-n-butylphenyl, 2,6 — —Λ 2'3 monomethylphenyl, 2,4_dimethylphenyl, 2-third methyldiyl '2,6_di Benzylphenyl, 2,4,6-trimethylphenyl, 2,6 · trifluoro / benz '4L dimethylphenyl, 3,5-digas-2,6-diethylbenzene • " And 2,6-wu (2,6_dimethylphenyl) phenyl, cyclohexyl and critical bite. —The ring system of formula ζ is preferred Is not 2, Bu alkylphenyl group or a fused polycyclic group eg, 1-naphthyl '2-naphthyl group, h Ji Feiji benzene 8+ and forest base.

The paper size is applicable (210x297 mm) 10 1238833 A7 B7 V. Description of the invention (7) Among the compounds of formula B and Z of the present invention, M is preferably Fe [II] or Co [II], and is further suitable for the present invention. The compound of the catalyst system is a skeleton unit containing formula T: R? 9

Rn-type Ding (please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs where M is Fe [II], Fe [III], Co [I], Co [II], Co [III], Mn [I], Mn [II], Mn [III], Mn [IV], Ru [II], Ru [III] or Ru [IV]; X means covalent or ionic bonding to transition Atom or group of metal M; T is the oxidation state of transition metal M, and b is the valence of X atom or group; R1 to R4, R6 and R29 to R32 are each selected from hydrogen, halogen atom, hydrocarbon group, substituted hydrocarbon group, hetero Hydrocarbyl or substituted heterohydrocarbyl; when any two or more of R1 to R4, R6 and R29 to R32 are hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted heterohydrocarbyl, these two or more may be bonded to form a Or multiple cyclic substituents. In the compound of the formula B of the present invention, M is preferably Fe [II]. Among the compounds of formula Z or T of the present invention, M is preferably Fe [II], Mn [II] or Co [II]. Examples of the X atom or group in the compounds of the formulae B, Z and T are halides such as chlorides, bromides; hydrides; hydrocarbyl oxides such as hafnium oxide, ethoxide, isopropoxide, phenoxide; carboxylate Acid salts such as formate,

、 1T This paper is again applicable to China National Standard (CNS) A4 specification (210X297 mm) 11 Printed by the Consumers' Cooperative of the China Provincial Bureau of Procurement Bureau 123833 A7 ^ ------ —_B7 V. Description of the invention (8 ) ^^ ·-acetates, benzylates; hydrocarbyl groups such as methyl, ethyl, propyl, butyl, octyl, decyl, phenyl, thylyl; substituted hydrocarbyls; heteronicotyl; toluates 'And trifluronate. Preferably, the amidine is selected from the group consisting of a halide, a hydride, and a nicotyl. Gasification is particularly preferred. The following are examples of nitrogen-containing transition metal complexes that can be used in the catalysts of the present invention: 2.6- Diethylsulfanylpyridinium (2,6 • diisopropylaniline) 2.6- Diethylsulfanylpyridine (2, Cardiodicumyl 2,6 · diethylanilide (2,6 • diisopropylaniline ... ^^ 2.6- Diethylsulfanylpyridinium (2-tert-butylaniline) FeCl2 Di Acetylpyridinium (2,3-dimethylaniline) 2.6- Diethylpyridinylpyridine (2 · methylaniline) FeCl2 2.6- Diethylpyridylpyridinium (2,4 · dimethyl) Aniline) FeC12 2.6- Diethylamidinopyridine (2,6_dimethylaniline) FeC12 2.6- Diethylamidinopyridine (2,4,6_trimethylaniline) 2.6-diadimine Vesicular hydrazone (2,6-dimethylaniline) FeCb 256-diadimine acetaminophen (2,6_diethylaniline) FeCl2 2.6-diadimine acetamidine (2,6_diiso Propylaniline) FeCl2 2.6-diadimine eridine (1 • naphthylamino) FeCl2 & 256-wu (ι, ΐ-diphenyl trace) cancer bite Feci2. The preferred complex of the present invention is 2 , 6-Diethylpyridinium pyridine (2,4,6-trimethylaniline) FeCl2. In yet another aspect of the present invention, the catalyst system may additionally include (4) days Lewis base. Neutral Lewis base is a Ziegler-Natta catalyst polymerization technology. This paper is based on the paper size of Guanjia County (CNS) A4 (210X297 mm). (Read the precautions on the back before filling in this. page)

1T #f 1238833 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of Invention (9) is well known. Examples of neutral Lewis bases suitable for use in the present invention are unsaturated hydrocarbons such as olefins or alkynes, first-, second-, and third-amines, amines, phosphatidamines, and phosphines , Phosphites, ethers, sulfur scales, eyes, carbonyl compounds such as esters, ketones, aldehydes, carbon monoxide and carbon monoxide, sulfonium, hydrazone and boroxene. Although olefins can be used as neutral Lewis bases, they are considered monomers or comonomers in the present invention and are not considered as neutral Lewis bases themselves. However, roasted examples of internalenes such as 2-butene and cyclohexene are considered neutral Lewis bases in the present invention. Preferred Lewis bases are tertiary amines and aromatic esters such as dimethylaniline, diethylaniline, tributylamine, ethyl benzate and benzyl benzate. In this particular aspect of the invention, the components (1), (2), and (4) of the catalyst system may be combined at the same time or in any predetermined order. However, if components (2) and (4) are compounds that have a strong interaction with each other, such as forming stable compounds, it is preferable to combine components (1) and (2) or components 0) and (4) in the initial step and then introduce Final order ingredients. Preferably, the components (1) and (4) are contacted before the component (2) is introduced. The amount of the ingredients (1) and (2) for preparing the catalyst system is suitable as described above for the catalyst of the present invention. The amount of the neutral Lewis base [ingredient (4)] is preferably to provide the ingredient (1). The ratio of the ingredient (4) is 100: 1 to 1: 100, and most preferably 1: 1 to 1:12. 〇Scope. The components (1), (2), and (4) of the catalyst system may be, for example, a combination of neat materials or a suspension or solution of materials in a suitable diluent or solvent (such as a liquid hydrocarbon), or if at least one of the components is Volatility utilizes the vapor combination of this ingredient. The components can be combined at any predetermined temperature. It is usually satisfactory to mix the ingredients at room temperature. Heat to a higher temperature, for example up to 120. (: If necessary, you can, for example, achieve a better mixing of the ingredients. Better than an inert atmosphere (such as anhydrous nitrogen) or true Z paper size A4 · (21 () χ29 — (Please read the precautions on the back before Fill out this page} Order 13 1238833 Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (10) The composition components (1), (2), and (4) below. If you want to use the catalyst in the monomer Materials (see below), a catalyst system containing ingredients (1), (2), and (4) can be pre-formed, and the monomer material can be impregnated with its solution; or one or more ingredients can be introduced into the monomer simultaneously or sequentially The material can be achieved. If necessary, the monomer material itself can have neutral Lewis basicity, and can be used as the component (4) or alternative component (4). An example of a monomer material with neutral Lewis's properties is poly ( Amine styrene baked) or a copolymer of styrene and amine styrene (ie, ethynyl aniline). The compound used as a catalyst in the catalyst system of the present invention may contain more than one kind if necessary The aforementioned transition metal compound. The catalyst includes, for example, 2,6-diethylpyridin (A mixture of 2,6-diisopropylaniline with ^ complex and 2,6_diethylsulfanylpyridinium (2,4,6-trimethylaniline) FeCL complex, or 2, 6_ Diethylpyridine (2,6-diisopropylaniline) coCl2 and 2,6-diethylpyridyl vesicles form (2,4,6-dimethylbenzylamine) FeCl; 2 mixture In addition to one or more defined transition metal compounds, the catalyst also includes one or more other types of transition metal compounds, such as the type of transition metal compounds used in the conventional Ziegler-Natta catalyst system, based on Metallocene catalysts, or thermally activated supported chromium oxide catalysts (such as Phillips type catalysts). The catalysts used in the present invention may be unsupported or supported on monomer materials such as silicon. Oxygen, methane or zirconium oxide, or supported on polymers or prepolymers such as polyethylene, polystyrene or poly (aminostyrene). If desired, the catalyst can be in situ in the presence of the monomer material Form; or the monomer material can be pre-impregnated or pre-mixed with one or more catalyst components at the same time or in sequence. If necessary, the catalyst can be supported on a heterogeneous catalyst, such as supported by dentine. Ziegler-Natta catalysts, Phillips (chromia) supported catalysts, or supported metallocene catalysts. Supported catalysts This paper applies Chinese National Standard (CNS) A4 specifications (210X297 mm) (Please read the notes on the back before filling this page)

1T # f— 14 1238833 V. The description of the invention (11) can be prepared, for example, by treating a transition metal compound with alumoxane in an appropriate inert diluent such as a volatile hydrocarbon, adjusting the granular monomer material into a slurry and evaporating the product. Removal of the volatile diluent was achieved. The amount of the monomer material may vary widely, such as 100,000 to 1 g per gram of metal present in the transition metal compound. Another aspect of the present invention includes the use of Formula 3, where each R is a CVC12 academy or autogen? To enhance the catalytic activity of the compound of formula B as defined above for the polymerization of 1-olefins. The present invention further provides a method for polymerization and copolymerization of thin smoke, which comprises contacting a dilute hydrocarbon monomer with a polymerization catalyst system under polymerization conditions, the polymerization catalyst system comprising (1) a formula B as defined above Compound (2)-an alkylaluminoxane activator 12 (3) A compound of formula A%, in addition to hydrazone, where each r is an alkyl group or a tooth atom, respectively. In a preferred method, the 'catalyst compound' is activated by alkylaluminoxane (2) when it is contacted with the monomer to be polymerized. The polymerization conditions are, for example, a solution phase, a slurry liquid phase or a gas phase. If the required catalyst system can be used to polymerize ethylene under high pressure / high temperature process conditions, the flying materials in the basin will form a melt on supercritical ethylene. The polymerization is preferably carried out under a gas-phase fluidized bed condition. The conditions of slurry liquid phase polymerization or gas phase polymerization are particularly useful for the production of Nanmiqi polyethylene. In these methods, the polymerization conditions can be batch continuous or semi-continuous. In the slurry-phase method and the gas-phase method, the catalyst is usually fed to the polymerization section as a granular solid. The solid is, for example, an undiluted solid catalyst system formed by the nitrogen-containing complex and B sheets from the applicable Chinese national standard 15 1238833 A7 B7 V. Description of the invention (l2) The activator printed by the Consumer Cooperative of the Central Standard Bureau of the Ministry of Economy , Or may be a solid complex alone. In the case to be described later, the activator may, for example, be supplied as a solution separately or fed to the polymerization section together with a solid complex. The transition metal complex component of a preferred catalyst system or a catalyst system for slurry polymerization and gas phase polymerization is supported on a monomer material. The best catalyst system was supported on monomer materials before the introduction of the polymerization section. Suitable monomer materials are, for example, silica, alumina, hammer oxygen, talc, kieseiguhr or magnesium oxide. The impregnation of the monomer material can be performed by conventional techniques, such as forming a solution or suspension of the catalyst component in an appropriate diluent or solvent, and preparing a slurry with the monomer material. In this way, the monomer-impregnated monomer material can then be separated from the diluent, for example, by filtration or evaporation techniques. In the slurry-phase polymerization method, the catalyst solid particles are fed into the polymerization section through a supported catalyst or are in the form of a dry powder or a slurry in a polymerization diluent. It is preferred that the particles be in a suspension feed to the polymerization diluent to the polymerization section. The polymerization section is, for example, an autoclave or similar reaction vessel, or a continuous loop reactor, for example, a reactor of the type well known for the manufacture of polyethylene by the Philips method. When the polymerization method of the present invention is carried out under slurry conditions, the polymerization is preferably performed at a temperature higher than 0, and most preferably at a temperature higher than 15 ° C. The polymerization temperature is preferably maintained below the temperature at which the polymer begins to soften or sinter in the presence of a polymeric diluent. If the temperature is the same as the temperature described later, the reactor may be fouled. Adjusting the polymerization over this specific temperature range can provide a useful means of controlling the average molecular weight of the polymer produced. Another useful means of controlling molecular weight is to carry out polymerization in the presence of hydrogen as a chain transfer agent. The higher the hydrogen concentration normally used, the lower the average molecular weight of the polymer produced. Use hydrogen as a means to control the average molecular weight of polymers or copolymers. Please read the note below before f 丨 this page ii 16 1238833

V. Description of the Invention (Π) ^ is usually a polymerization method applied to the present invention. For example, hydrogen can be used to reduce the average knife 1 of polymers or copolymers prepared using pore-phase aqueous or liquid-phase polymerization conditions. The amount of hydrogen that has been reported to have a predetermined average molecular weight can be determined by simple trial and error J polymerization test. Printed by the Consumer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs J. I — I ----— (Please read the precautions on the back before filling this page )

1T The polymerization method of the present invention can obtain polymers and copolymers with significantly high productivity. Special polymers (capacity is based on the weight of the polymer or copolymer produced based on the weight of the nitrogen-containing transition metal complex used per unit catalyst system). Quantity). For example, Λ indicates the relatively small amount of transition metal complexes consumed by the commercial method using the Shuming method. It also means that # the polymerization method of the present invention is operated under polymer recovery conditions without using a catalyst separation step [so that the catalyst or its residue is left in the polymer (such as appears in most semi-commercial slurry and gas phase polymerization methods, The content of the transition metal complex in the polymer is extremely low. Practical experiments using the catalyst of the present invention show that the polymerization of ethylene under slurry polymerization conditions can obtain a granular polyethylene product, which contains the catalyst to dilute the transition metal into a transition metal. The concentration is reduced to, for example, 1 ppm or less. "Medium" ppm "is defined as the weight ratio of the transition metal parts per million parts by weight of the polymer. Thus, the polyethylene produced in the polymerization reactor by the method of the present invention contains The medium is diluted with polyethylene to a transition metal content of, for example, in the range of 1 to 0.0001 ppm, preferably 1 to 0.00 m. The nitrogen-containing iron complex catalyst according to the present invention is used in, for example, a slurry. Polymerization can obtain a polyethylene powder containing iron at a concentration of, for example, 1.03 to 0.11 parts by weight of iron relative to the mother million parts of polyethylene. The monomers suitable for the polymerization method of the present invention are, for example, ethylene and acrylic acid. Butene'hexene, methyl methacrylate, methyl acrylate, butyric acid acrylate 'acrylonitrile, vinyl acetate and styrene. The preferred homopolymerization method is 17 1238833 A7 B7 V. Description of the invention (i) It is ethylene and propylene. The catalyst can also be used to copolymerize ethylene with other 丨 _hydrocarbons such as propylene, 1-butene, 1-hexene, 4-methylpentene-1 and octene. Operation methods of gas phase polymerization It is well known in the industry. These methods usually include agitating (such as stirring, shaking, or fluidizing) a catalyst bed, or a target polymer bed containing a catalyst (that is, a polymer having the same or similar physical properties as those intended for the polymerization process). Polymer) 'and at least a portion of the gas phase monomer stream is fed therein, and the feeding conditions are such that at least a portion of the monomer polymerizes when it contacts the catalyst of the bed. The bed is usually by adding a cooling gas (such as circulating gaseous monomer) or volatile Liquids (such as volatile inert hydrocarbons, or gaseous monomers that have been condensed to form a liquid) Cooling. Polymers produced in the gas phase process or separately from the gas phase process can be directly formed into solids in the polymerization section, or contain no or substantially Contains liquid. As is well known in the industry, if gas is allowed to undergo the polymerization section of the gas phase polymerization method, the amount of polymer present in the liquid relative to the polymerization section is small. This is the opposite of the "solution phase" method, where the polymer is dissolved in a solvent , And the opposite of the "slurry phase" method, in which the polymer is formed as a suspension in a liquid diluent (read the precautions on the back before filling this page)

Printed by 1T Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs

The gas phase process can be carried out under batch, semi-continuous or so-called "continuous" conditions. When operating preferably under the following conditions, the monomers are continuously circulated to the actuated polymerization section containing the polymerization catalyst, 'Supplementary sheet is used to replace the polymerized monomers', and continuous or intermittent & The rate of product formation rate is the polymer produced by the withdrawal of the polymerization section, and fresh catalyst is added to the polymerization section to replace the catalyst withdrawn from the polymerization section along with the generated product. In a preferred embodiment of the emulsion polymerization method of the present invention, the gas-phase polymerization conditions are preferably gas-phase fluidized-bed polymerization conditions.

This paper size applies Chinese National Standard (CNS) A4 · (2IG > ^^

1238833 A7

Operating methods for the manufacture of gas phase fluidized bed processes of polyethylene and ethylene copolymers are well known in the industry. This process can be performed, for example, in a vertical cylindrical reactor equipped with a porous distribution plate to support the bed, and the incoming fluidized gas stream is passed through the bed. A fluidizing gas is circulated through the bed for removing the heat of polymerization from the bed and supplying the polymerization monomer to the bed. As such, the fluidizing gas usually contains monomers along with several inert gases (such as nitrogen) and selective hydrogen as molecular weight modifiers. The hot fluidized gas sent from the top of the bed is selectively guided through the deceleration section (which can be a cylindrical part with a wide diameter of the reactor), and if necessary, the cyclone and filter are used to pass fine solid particles Entrainment in the air flow. The hot gas is then directed to a heat exchanger to remove at least part of the heat of polymerization. The catalyst is preferably fed continuously or at regular intervals. At the beginning of the process, the bed contains a fluidizable polymer, which preferably resembles the target polymer. Polymers are continuously produced in the bed by polymerizing monomers. The device is preferably equipped with a polymer discharged from the bed continuously or at regular intervals to maintain the fluidized bed at a predetermined height. The method is usually carried out at a relatively low pressure such as 10 to 50 bar, but it can also be carried out at a temperature of up to 100 bar; and at a temperature of 50 to 120 ° C, for example. The bed temperature is maintained below the sintering temperature of the fluidized polymer to prevent agglomeration problems. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs In the gas-phase fluidized bed method of polymerizing olefins, the heat generated by the exothermic polymerization reaction is usually removed by the polymerization section (ie, the fluidized bed) using the aforementioned fluidized gas stream. The thermal reactor gas sent from the top of the bed is directed through one or more heat exchangers where the gas is cooled. The cooled reactor gas is circulated to the bottom of the bed along with any supplementary gas. In the gas-phase fluidized bed polymerization method, it is desired to provide additional cooling of the bed by feeding volatile liquid to the bed (thereby improving the space-time yield of the process). The feed condition is that the liquid volatilizes in the bed. 1 ____ '_ This paper is printed from the applicable Chinese National Standard (CNS) M specification (21 () > < 297 Gongchu) · -19-1238833 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 i. Invention Description ( 16) "Latent heat" effect to absorb additional polymerization heat from the bed. When the heat circulating gas from the bed enters the heat exchanger, the volatile liquid condenses out. In one embodiment of the present invention, the volatile liquid is separated by the circulating gas and introduced into the bed again. Thus, for example, volatile liquids can be separated or sprayed on the bed. In another embodiment of the present invention, the volatile liquid is circulated to the bed together with the circulating gas. Such a volatile liquid can be condensed in the fluidized gas stream sent from the reactor, and can be circulated to the bed with the circulating gas' or can be separated by the circulating gas and misted into a bed. Methods for condensing liquid in a circulating gas stream and returning a gas-entrained liquid mixture to the bed are described in EP-A-0089691 and EP-A-0241947. Preferably, the condensed liquid is reintroduced into the bed separate from the circulating gas using the method described in U.S. Patent No. 5,541,270, the teaching of which is incorporated herein by reference. -When the catalyst of the present invention is used under a gas phase polymerization condition, the catalyst or one or more components for forming the catalyst may be introduced into the polymerization reaction section in a liquid form, such as a solution in an inert liquid diluent. Thus, for example, the transition metal component, or the activator component, or both components can be dissolved or slurried in a liquid diluent and fed to the polymerization section. Under these conditions, it is preferred that the liquid containing these components is sprayed in fine droplets on the polymerization section. The diameter of the droplets is preferably in the range of 1 to 1000 microns, and EP_A_0593083's teachings are described herein for reference 'to reveal a method for introducing a polymerization catalyst into a gas phase polymerization. The method disclosed in 0593083 is suitable for the polymerization method of the present invention if necessary. The present invention is illustrated by the following examples. Examples Example 1 shows the preparation of novel iron compounds (see formula D below), and examples of this book (please read the notes on the back before filling this page) Order II · 20 1238833 A7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ~~ -----—— ____B7 V. Description of the invention (17) 3 shows the preparation of novel cobalt compounds (see formula 〖), each compound is according to the present invention. In the examples, all air / water-sensitive materials are handled in standard vacuum, inert atmosphere (nitrogen) pipelines using standard Hiram tubing technology, or in an inert atmosphere glove box. ± M1 Intermediate A [2,6-diethylstilbidine (2,6-diisopropylaniline)] via intermediate B [2,6-diethylstilbidine] and intermediate c [2,6-Diisopropylaniline] prepared by reaction. Intermediate A is then reacted with vaporized ferrous iron in butanol to obtain a compound of formula D. Soil_interstitial A is used based on the relevant preparation procedures (EC · Alyea and PH Meirell, Synth. React. Inorg, Metal-Org. Chem ·, 1974, 4, 535): _2,6-diisopropylaniline (3.46 ml, 18.4 mmol) was added dropwise to a solution of 2,6-diethylpyridin (1.50 g, 9.2 mmol) in absolute ethanol (25 ml) Aniline and 2,6-diethylpyridin are derived from the Aldrich reaction, the former being freshly distilled before use]. A few drops of glacial acetic acid were added and the solution was refluxed for 48 hours. The solution was concentrated to a half volume and cooled to -78 ° C to obtain intermediate A as a pale yellow crystal (80% p calculated c33H43N3: C, 82 · 3; Η, 8.9; N, 8.7; measured value: c , 81.9; H, 8.5; 8.7 〇 / 〇. FABMS: M + (481). 4 NMR (CDC13): 8.6-7.9 [m, 3Η, C5H3N], 7.2-6.9 [m, 6H, C6 (CHMe2 ) H3], 2.73 [sept, 4H, CHMe2], 2.26 [s, 6H, C5H3N (CMeNAr) 2], and 1.16 [m, 24H, CHMe2] o FABMS is fast atomic impact mass spectrometry. This paper is in accordance with Chinese national standards (CNS) Α4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page)

-m 1 I ^ in ί · 21 Ϊ238833

i 'Explanation (18)

—MtwMW · ϋι ϋ · — Mi n-ϋ ftn HI —ϋ i_l i_a— (Read the precautions on the back before filling in this page) Orders and Lithos [2,6-Diethylpyridinium hydrazone (2 · 6_ Two different rain-based mochi servants ... ^! Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economics and Production

FeCl2 (0.24 g; 1.89 mmol) was dissolved in 80. 〇 Hot n-butanol (20 ml). A suspension of 2,6-diethylamidinocarboxamidine (2,6-diisopropylaniline) (0 92 g, 1.89 mmol) in n-butanol was added dropwise. The reaction mixture turned blue. After stirring at 80 ° C for 15 minutes, the reaction was allowed to cool to room temperature. The reaction volume was reduced to several liters, and the product (blue powder) was precipitated by adding petroleum ether (40/6), which was then washed three times with 10 ml of petroleum test (40/60). The yield was 0-93 g (81%). Mass spectrum: m / z 607 [M] +, 572 [M-C1] +, 482 [M-FeCl2] +. Analytical calculation value · C33H43N3FeCl2: C, 65.41; H, 7 · 12; N, 6.91 ¥ Paper size applies to China National Standard (CNS) A4 (210X297 mm) ~~ ----- 22 1238833 A7 B7 V. Invention Note (19). Found: C, 64.19; H, 6.90; N, 6.70. Example 3_2 Diethyl alcohol-based cancer (diisopropyl glucosamine) coCi, · Preparation of formula kappa monochloride (¢ 0 (^ -0.057 g; 0.44 mol) dissolved in 80 ° c Hot n-butanol (10 ml). Intermediate A [2,6-diethylfluorenyl vesicular (2,6-monoisopropylaniline)] (0.21 g; 0.44 mol) in n-butanol. After stirring at 80 for 15 minutes, the resulting reaction product was allowed to cool to warm. The reaction volume was reduced to a few milliliters and petroleum ether (40/6/6) was added. Precipitated product. The powdery precipitate of olive green was washed 3 times with a whole portion of 10 ml of petroleum ether (4/6/6). The cobalt complex (formula K-see below) yielded 018 g (67% of theory). . Mass spectrum shows m / z 575 [M-C1] +, 538 [M-2C1] +. (Please read the precautions on the back before filling this page)

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Preparation Example of AZ to 9-Iron Complex Printed by the Consumer Cooperatives of the Central Bureau of Quasi-Staff of the Ministry of Economic Affairs 7 The procedure for the preparation of diethylpyridinidine (2,6 · dimethylbenzylamine) is the same as Example 4.1 , But use 2,4-difluorenylaniline instead of 2-tert-butylaniline. The yield is 75% of theory. The paper size is suitable for financial matters and household materials (cns) A4na (2 offers 297). 23 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 1238833 A7 ____B7 V. Description of the invention (20) NMR (CDCI3): 8.41? 7.905 7.055 6.9〇 6.55 (m? 9H5 ArH, pyrH), 2.36 (m5 6H, N = CCH35 6H, CCH3), 2.13 (s, 6H, CCH3) Mass spectrum: m / z 369 [M] +. Z: 2 · 2? 6 · —_Acetylene bite bite (2,4 · dimethyl face makeup * 卞 The procedure is the same as in Example 4.2, but using 2,6-diethylpyridine (2 , 4-Dimethylaniline) instead of 2,6-diethylfluorenylpyridinium pyrene (2 · third butylaniline). The yield is 75% of the theoretical value. Mass spectrum: m / z 496 [M] '461 [ M-C1] +, 425 [Μ · α2] +. Example 8 m, 6 · Diethylpyridinidine (2,6_dimethyl formaldehyde, and the preparation procedure is the same as in Example 4.1, but using 2 , 6-Dimethylaniline replaced 2-tert-butylaniline. Yield was 78% of theory. 4 NMR (CDC13): 8.48, 8.13, 7.98, 7.08, 6.65 (m, 9H, ArH, pyrH), 2 · 25 (s, 6H, N = CCH3), 2.05 (m, 6H, CCH3). Mass spectrum: m / z 369 [M] +. L2-2,6-diethylsulfanylpyridinium (2, The preparation procedure of 6-dimethylmoscaridine was the same as in Example 4.2, but 2,6-diethylamidinopyridine (2,6-dimethylaniline) was used instead of 2,6-diethylpyridine. Thallium (2-tert-butylaniline). Yield is 78% of theory. Mass spectrum: m / z 496 [M] +, 461 [M-C12] +, 425 [M-C12] +. Example 9 22 The condensed diethylpyridinidine (2A6-trimethylbenzylamine) is the same as in Example 4.1, but using 2,4,6- Methylaniline in place of 2 of this paper from the appropriate fiscal Guan County (CNS) A4 ^ (21Gx297 public Chu) " - - -24 - (Please read the Notes on the back to fill out this page)

1238833 Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of Invention (21) Dibutyl benzylamine. The yield is 60% of theory. NMR (CDC13): 8.50, 7.95, 6.94 (m, 7H, ArH, pyrH), 2.33 (s, 6H, N = CCH3) 5 2.28 (s, 6H, CCH3), 2.05 (s, 12H, CCH3) o Mass spectrum : M / z 397 [M; I +. The procedure for the preparation of ethynylpyridinium (2,4,6-trimethylbenzylamine ^ FeCh) is the same as in Example 4.2, but 2,6-diethylpyridinylpyridine (2,4,6 · dipyridine) Aniline) instead of 2,6-diethylsulfanylpyridinium hydrazone (2-tert-butylaniline). Yield is 64% of theory. Mass spectrum: m / z 523 [M] +, 488 [M-C12] +, 453 [M-C12] +. Examples 14-25 These examples are a series of experiments in which ethylene or ethylene / i-hexene is used under the pressure of 10 bar ethylene to use the catalyst of the present invention in the "slurry" polymerization conditions Polymerization. The transition metal complexes used as catalysts in Examples 14 to 25 are as follows: The complexes in Examples 14 and 15 are 2,6-diethyl acetophenone (2,6 · diisopropylaniline FeCh was prepared as described in Example 1 (compound of formula D). The complex of Examples 16 to 20 was 2,6-diethylfluorenylpyridinium (2,6-dimethylaniline) FeCl2, such as Prepared as described in Example 8. The complex of Example 21 is 2,6-diethylfluorenylpyridinium (2,4-dimethylaniline) FeCl2, which was prepared as described in Example 7. Examples 22 to 24 The complex is 2,6-diethylfluorenyl cancer bite (2,4,6-trimethylaniline) FeCl2, which was prepared as described in Example 9. (Please first (Read the notes on the back and fill out this page)

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25 1238833 A7 B7 V. Description of the invention (22) The complex of Example 25 is 2,6-diethylfluorenylpyridinium (2,6-diisopropylaniline) CoCl2, as in Example 3 (Formula K) The preparation. Catalyst activation The transition metal complex is dissolved in toluene (previously dehydrated with sodium metal) in a nitrogen atmosphere, and an activator (auxiliary catalyst) solution is added to it at ambient temperature. The mixture was stirred at room temperature, and then the whole was transferred to the injection unit of the polymerization reactor. The amount of catalyst-activated reactants is set in the table below. All operations were performed under nitrogen unless otherwise specified. "MAO" is methylalumoxane (1.78 M in toluene, supplied by Witco). "MMAO" is modified methylaluminoxane (10% w / w in heptane, supplied by Witco). It is used as purchased. Triisobutylaluminum (Al (iBu) 3) was supplied by Yadeli as a 1M solution in toluene. * ^ m ί! 1-- -1- I--I (Please read the precautions on the back before filling out this page) Order example number Metal complex] (mg) [metal] (micro㈣) Catalyst (ml) [A1] (gang [Fe]: [Al] toluene (ml) Molar concentration of solution (M) 14 3 5 MAO 2.78 5 1: 1000 20 0.0025 15 3 5 MAO 2.78 5 1: 1000 20 0.0025 16 1.5 3 MAO 1.70 3 1: 1000 10 0.0025 17 1.5 3 MMAO 3.93 3 1: 1000 10 0.0025 18 1.5 3 MAO 1.70 3 1: 1000 50 0.006 19 1.5 3 MAO 1.70 3 1: 1000 10 0.0025 20 1.5 3 MAO 0.17 3 1: 1000 10 0.0025 21 1.5 3 MAO 1.70 3 1: 1000 10 0.0025 22 3 6 MAO 3.22 6 1: 1000 20 0.003 23 1.5 3 MAO 1.61 3 1: 1000 10 0.003 24 3 6 MAO 0.32 0.3 1: 100 20 0.003 25 3 5 MAO 2.78 5 1: 1000 20 0.0025 Polymerization test printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Polymerization test The reaction reagent used is ethylene grade 3.5 (Air Products Company) This paper applies Chinese national standard (CNS) A4 Specifications (210X29? Mm) 26 1238833 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (23) Supply, hexene (Supplied by Yardley) Distilled in sodium / nitrogen and triisobutylaluminum (1M in hexane, Yardley). Ethylene polymerization 1 liter reactor under nitrogen flow for more than 85r at least 1 hour. Then react The reactor was cooled to 50 ° C. Isobutane (0.5 liters) and triisobutylaluminum 'and the reactor were placed under a nitrogen atmosphere. Ren Shaojii was removed from the reactor for at least 1 hour. Ethylene was introduced into the reactor until it reached Overpressure was predetermined, and then the catalyst solution was injected under nitrogen. The reactor pressure was kept constant by the addition of additional ethylene during computer control during the polymerization. The polymerization time was i hours. At the end of the operation, the reactor contents were separated to acidify methanol ( 50 ml of hydrochloric acid / 2 5 liters of methanol), washing with water / ethanol (4: 1 v / v), and vacuum dehydration at 40 ° C for 16 hours. Copolymerization of Lene / 1 · hexene (Example 19) 1 A one-liter reactor was baked at greater than 85 ° C for at least 1 hour under a nitrogen flow. The reactor was then cooled to 50 ° C, and isobutane (0.5 liters), 1-hexene and triisobutylaluminum were added, and the reactor was placed under a nitrogen atmosphere. Allow any alkylaluminum to remove the poison in the reactor for at least 1 hour. Ethylene was introduced into the reactor to a predetermined overpressure, and then the catalyst solution was injected under nitrogen. The reactor pressure was kept constant during the polymerization process by computer controlled ethylene addition. The polymerization time was i hours. At the end of the operation, the contents of the reactor were separated, washed with acidified methanol (50 ml of hydrochloric acid / 2.5 liters of methanol) and water / ethanol (4 ·· 1 v / v), and dehydrated under vacuum at 40 ° C for 16 hours. This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

1T 27 1238833 V. Description of the invention (24) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The data obtained from the A7 B7 polymerization test are shown in the table below. Table example number [metal] (micro · metal / shoxane ratio CA (bar) hexene (ml) Al (iBu) (ml) polymerization temperature (degree K) polymer (g) activity (g / mmole M / h / b) 14 0.3 1: 1000 10 0 3 323 26.9 5430 15 0.3 1: 1000 10 0 3 298 45.0 9090 16 0.3 1: 1000 10 0 3 323 56.5 9340 17 0.3 1: 1000 10 0 3 323 57.4 9510 18 0.13 1: 1000 10 0 3 323 3.3 2540 19 03 1: 1000 10 50 3 323 67.6 16690 20 0.3 1: 1000 10 0 3 323 74.5 12310 21 0.3 1: 1000 10 0 3 323 7.8 1280 22 0.3 1: 1000 10 0 3 323 63.1 11020 23 0.06 1: 1000 10 0 3 323 55.7 48690 24 0.3 1: 100 2 0 2 323 18.21 15150 25 0.3 1: 1000 10 0 3 323 3.7 450 The molecular weight data of the polymers obtained in Examples 14 to 25 are shown below Table Example Number Mw Μη Μ Peak PD 14 611000 64000 246000 9.5 15 857000 212000 415000 4.0 16 242000 9600 16000 25.3 17 278000 5700 1300 48.7 18 366000 50000 102000 7.3 19 377000 6500 43000 57.7 21 470 360 370 1.3 25 14000 4200 12000 3.3 Examples 26 and 27 Gas phase polymerization test using a supported catalyst Examples 26 and 27 illustrate the use The catalyst of the invention is supported on a siloxane monomer material. Example 26 uses 2,6-diethylfluorinated vesicular pyridine (2,6-diisopropylaniline). The paper size is applicable to Chinese National Standard (CNS) A4 (210X297). Mm) (Please read the notes on the back before filling in this page)

28 1238833 A7 B7 V. Description of the invention (25)) FeCl2, and Example 27 uses 2,6-diethylfluorenylpyridinium (2,4,6 · trimethylaniline) FeCh as the transition metal complex compound. (Read the precautions on the back before you fill in this page.) Example 26 Catalyst-supported borrowing 2.6- Diethylpyridinidine (2,6 • diisopropylaniline) FeCi2 was prepared as described in Example 1. Shi Xi oxygen (1.03 g of ES 70, supplied by Crosfield) has been heated under a flow of nitrogen at 700 ° C, placed in a Chiron tube, and toluene (10 ml) was added. The mixture was heated to 50 ° C. 2,6-Diethylfluorinated vesicular pyridine (2,6-diisopropylaniline) Feci: (0.036 g) in a solution of toluene (10 ml) was added methylalumoxane (5 ml, 1 · 78M in toluene, supplied by Witco). The mixture was at 50 ° C. (: Heated 'and then moved to the Shixi oxygen / toluene mixture. The Shixi oxygen / MAO / toluene mixture was maintained at 50 ° C with periodic stirring over a period of hours! Then, at 65, it was vacuumed to remove toluene to obtain a free-flowing powder. Example 27 Supported by the Ministry of Economic Affairs of the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives printed 2.6- Diethylpyridinidine (2,4,6-trimethylaniline) Feci2 was prepared as described in Example 9. Siloxane ( 1.38 g of ES 70, supplied by Crosfield) has been heated under flowing nitrogen at 700 c, placed in a Schlenk tube and toluene (10 ml) is added. To a solution of 2,4,6-trimethylaniline) FeCl2 (〇41 g) in toluene (1 ml) was added methylalumoxane (132 l, 1.78 M in toluene, supplied by Witco). It is heated for 30 minutes to dissolve as much iron complex as possible. Then the solution is transferred to silica / toluene. Silicon 29 1238833 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 5. Invention Description (26) Oxygen / MAO / The formazan mixture was maintained at 40 ° C with regular stirring for 30 minutes' followed by vacuum removal at 40 ° C Toluene was obtained as a free-flowing powder. The solids were analyzed to obtain 16.9% w / w A1 and 0.144% w / w Fe. Polymerization Tests-Examples 26 and 27 The reagents used in the polymerization tests were: Hydrogen 6.0 grade (supplied by Air Products); Ethylene 3.5 (supplied by Air Products); hexene (supplied by Yadeli) distilled in sodium / nitrogen; anhydrous pentane (supplied by Yadeli); alumino-aluminum (supplied by 2M in hexane's Yadeli); And triisobutylaluminum (1M in hexane, supplied by Atelier). The 3 liter reactor was baked under flowing nitrogen at 77-85 ° C for at least 1 hour, and then powdered sodium chloride (300g, at Pre-dehydration under vacuum, i60 ° C, > 4 hours). Sodium chloride was used as a fluidizable / stirable starting feed powder for gas phase polymerization. Trimethylaluminum (3 ml, 2M in hexanes) ) Add to the reactor, and cover it under a nitrogen atmosphere. Any burned aluminum is used to remove the poison in the reactor for 1 / 2-1 hours, and then use 4 times 4 bar nitrogen to sweep the ventilation. The gas-phase combination for polymerization is introduced into the reactor And then preheated to 77 ° C, and then injected the catalyst composition. The catalyst (0.18-0.22 g) was injected under nitrogen, then The temperature was adjusted to that. During the polymerization, the ratio of hexene and / or hydrogen to ethylene was monitored by a mass spectrometer and the balance was adjusted as needed to keep it constant. The polymerization test lasted for 2 hours and was then purged with nitrogen from the reactor. The reaction was terminated by lowering the temperature to below 3 Q. The resulting polymer was washed with water to remove sodium vapor, then washed with acidified methanol (50 ml of hydrochloric acid / 2 · 5 liters of methanol), and finally with water / ethanol (4 ·· 1 v / v) was washed. The polymer was dehydrated at 4 (rc for 16 hours under vacuum). Several runs were performed with the catalysts of Examples 26 and 27 using various operating conditions. All aggregation test

In --.------- (Please read the notes on the back before filling this page) Order

-30-1238833

A B Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (27) The tests were performed at a polymerization temperature of 80 ° C and an ethylene pressure of 8 bar. The polymerization conditions are listed in the following table. Table example / Round metal (% w / w) MAO / metal ratio to other auxiliary catalysts / h2 (bar) Hexene (bar) Pentene (bar) Operating time (minutes) Active gram / millimolar M / h / b 26.1 0.21 150 氺 氺 氺 * 氺 氺 氺 氺 氺 *** 75 77 26.2 0.21 150 氺 氺 氺 本 氺 氺 氺 氺 0.195 氺 * 氺 氺 90 77 26.3 0.21 150 ΤΑΜ / 6 氺 氺 氺 氺 ♦ 氺 氺 氺 *氺》 ► 氺 60 149 26.4 0.21 150 ΤΜ / 6 0.75 Script 60 318 27.1 0.144 300 氺 氺 氺 氺 氺 氺 氺 氺 氺 氺 氺 氺 氺 氺 氺 氺 60 611 27.2 0.144 300 ΤΜ / 6 0.5 氺 氺 氺 氺 氺 氺 氺 氺 60 832 27.3 0.144 300 ΤΑ / 6 0.5 0.2 氺 氺 氺 氺 60 1054 27.4 0.144 300 ΤΑ / 6 0.5 氺 氺 氺 氺 2.4 60 1800 27.5 0.144 300 TiBA / 3 氺 氺 氺 氺 氺氺 氺 氺 氺 ψ 氺 氺 60 713 27.6 0.144 300 氺 氺 氺 氺 3 luck 氺 氺 氺 氺 氺 氺 60 501 27.7 0.144 300 * 44 * * 氺 氺 * 0.86 氺 氺 氺 * 60 418 molecular weight of polymer product The information is shown in the table below. Round Catalyst Mw Μη Μ Peak Polydispersity 26.1 Example 26 26.2 Example 26 892000 106000 332000 8.4 26.3 Example 26 278000 8400 95000 33.0 26.4 Example 26 195000 7200 43000 27.0 27.1 Example 27 324000 9300 134000 34.6 27.2 Example 27 223000 18000 42000 12.3 27.3 Example 27 77000 6000 21000 12.8 27.4 Example 27 154000 5700 28000 26.9 27.5 Example 27 207000 4800 86000 43.1 27.6 Example 27 69000 5400 14000 12.7 27.7 Example 27 127000 14000 51000 9.3 (Please read the precautions on the back before filling this page) This paper size applies China National Standard (CNS) A4 specification (210X 297 mm) 31 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 1238833 A7 _____B7 V. Description of the invention (28) Example 32 11 · 1-Large scale catalyst ingredients Oxygen (20 kg) (ES 70 grade, supplied by Crosfield, has been dehydrated under flowing nitrogen for 8 hours) was slurried in hexane (110 liters), and Rokko was added at 50 ° C with stirring. Disilazane (30 mol) (supplied by Fluka). Anhydrous hexane (120 liters) was added with stirring, and the solids were allowed to settle. The supernatant was removed by decantation and anhydrous hexane (130 liters) was further added with stirring. Hexane washing was repeated 3 more times. Dibutyl ball (30 mol) was added, FMC was supplied, and at 50 ° C. 〇 Stir for 1 hour. Add tertiary butyl chloride (60 moles) and stir at 5 (rc) for 1 hour. This slurry is stirred at 50 ° C for 2 hours, and titanium tetraoxide (3 moles) and titanium tetra-n-propionate are added. (3 moles) of equal molar mixture, and then washed 5 times with anhydrous hexane (130 liters). The slurry was dehydrated under a flowing nitrogen stream to obtain a solid silicone-supported Qixile catalyst component. Jin Guang of the present invention Preparation of Greiger components and transition metal compounds ^ Methylaluminoxane ("ΜΑΟ", 10.2 mmol) was added as a 10% wt in toluene solution (supplied by Witco) to 2, as prepared in Example 9, 6_Diethyl alcohol cancer bite (2,4,6-dimethylaniline) FeCh suspension (0.07 mmol in 5 ml of anhydrous toluene), and the mixture was shaken for 5 minutes. Then this solution Add to 20 g of the silica-supported Ziegler catalyst prepared as described above (Example 321), shake the mixture at 20 C for 2 hours, then remove the solvent under reduced pressure at 20 ° C to obtain a mixed catalyst that flows freely. Powder. Use a mixed catalyst to prepare a 3 liter ethylene / hexanox mixture. The reactor is equipped with a spiral stirrer and heated to ^^ calendar 丨 hours. Applicable to China National Standard (CNS) Α4 specification (210 × 297 mm) J .----- Clothing— (Please read the precautions on the back before filling this page) Order 32

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs through which dry nitrogen flows. The temperature was lowered to 50 cC, and then anhydrous sodium vaporization (300 g) was added to a trimethylaluminum (TMa) solution (2 ml, 2 mol TMA in hexane), and the reactor was heated at 85 ° C for 2 hours. The reactor was purged with nitrogen, cooled to 50 ° C and TMA solution (3 ml, 2 mole TMA in hexane) was added. The temperature was raised to 77 ° C and hydrogen (0.5 bar) and ethylene (8 bar) were added before 1-hexene (2.6 ml). The reaction was started by injecting the mixed catalyst (0.20 g) prepared as above into the reactor. The temperature was maintained at 0 ° C, and ethylene was added to maintain a constant pressure. Monitor the gas phase with a mass spectrometer, and add hydrogen and 1-hexene as needed to keep the gas phase concentration of each component constant. The polymerization was carried out for 90 minutes. The polymer was washed with water to remove sodium chloride, and then washed with acidified methanol (50 liters of hydrochloric acid / 2.5 liters of methanol) 'and finally water / ethanol (4: 1 v / v). The polymer was dehydrated under vacuum at 40 ° C for 16 hours. A hi gram of anhydrous polymer was produced. The polymer has a broad molecular weight distribution (determined by gel permeation chromatography). The polydispersity (Mw / Mn) was 28.5. Example 33 L. 1- · 1-Pre-impregnation of monomer with activator compound Unless otherwise stated, all operations described below were performed under a nitrogen atmosphere. Silicon oxide (Crosfield grade ES70X) was heated under flowing nitrogen at 250 ° C for 16 hours. A sample of silicon dioxide (2.5 g) was placed in a Schlenk tube, and 12.1 ml of 1.78 M fluorenyl aluminoxane was added to MAO (supplied by Witco) to form a slurry. The slurry was stirred at 50 ° C for 4 hours, and then left at room temperature for 10 days. Above the silica, the supernatant was removed, and the silica / MA0 was washed 3 times at room temperature with toluene (3 × 10 亳 liters) ’each time the supernatant was removed. jj · 2-Main load catalyst This paper size applies to China National Standard (CNS) Α4 specification (210X297 mm) J .---.------- (Please read the precautions on the back before filling in this page)

1T 33 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 1238833 A7 B7 V. Description of the invention (30) ~~ 2,6-Diethylpyridinium pyrene (2,4,6-trimethylaniline) Iron (0.101 g) (prepared as described in Example 9) was slurried at room temperature in toluene (20 ml) and added to silica / MAO. The mixture was occasionally shaken for 1 hour. Remove the supernatant and silica / MAO / Fe complex and wash with toluene until the filtrate is colorless. The solid was dried under vacuum at 50 ° C. 33.3-Gas phase polymerization of ethylene. A 3 liter reactor was baked at 77 ° C for at least 1 hour under a stream of nitrogen, followed by the addition of sodium chloride (300 g, particles smaller than 1 mm in diameter, under vacuum 160. It was pre-dried 'for more than 4 hours. ). Vaporizing sodium is simply used as the standard "feed powder" for gas phase polymerization reactors. Trimethylsaucer (3 ml, 2M in hexane, supplied by Adelley) was added to the reactor and then closed. Any alkyl aluminum was removed from the reactor for 1/2 hour, and then the reactor was vented by continuous pressure and sweeping the reactor with 4 bar nitrogen. Ethylene (grade 3.5, supplied by Air Products) was added to the reactor to obtain a pressure of 77 ° (: 8 bar, followed by catalyst injection. The supported catalyst (0.215 g) prepared as described in Example 33.2 was under nitrogen. Injected into the reactor, and then adjusted the temperature to 80 ° C. The polymerization was continued for 5 hours, and then the nitrogen was used to sweep the reactor to remove the ethylene to stop the reaction, and the temperature was lowered to less than 30 ° c. The polymer was washed with water to remove sodium gasification Then, it was washed with acidified methanol (50 ml of hydrochloric acid / 2.5 liters of methanol), and finally washed with water / ethanol (4: 1 v / v). The polymer was dehydrated under vacuum at 40 ° C for 16 hours. 161 g of anhydrous polymer was produced Examples 35 to 38 illustrate the preparation of a supported catalyst according to the present invention and its use in the polymerization of ethylene under the conditions of "slurry" polymerization. Example 35 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297) (Mm) 1 ^-nn Ί— I-n III {Read the notes on the back before filling in this page j 1T < • II I—J. 34 Employees' Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, printed milk 8833 A7 ^ ____ B7 and, Ming (^ one'- two second Fructus bite (2,4,6-trimethyl jasmine) diglucose 铖 * $ ^ 4A0 / silica gas preparation stone Xi oxygen monomer material (grade ES70X, supplied by Crossfield) at 250. (: mobile It was heated under nitrogen for 16 hours. The silicon oxide sample was placed in a Schlenk tube, and 121 liters of 1.78M methylalumoxane (supplied by "MAO" Witco) was added thereto to form a slurry. The slurry was heated at 50 C for 4 hours. Then, it was left to stand at room temperature for ι0 days. Then the supernatant liquid above Shi Xi oxygen was removed, and Shi Xi oxygen / MA0 was washed 3 times at room temperature with toluene (10 ml), and the supernatant was removed each time. Liquid. 2,6-Diethylpyridinium pyridine (2,4,6-dimethylaniline) digasified iron complex (0101 g) in toluene (20 ml). Make a slurry and add it to Shixi Oxygen / MA0. The mixture is occasionally searched for 1 hour. The supernatant is removed, and the formed silica-supported hydrazone is washed with toluene and mixed with toluene to the original washing solution (light orange). It became clear and colorless. The resulting silica-supported catalyst solid was dehydrated under vacuum at 50 ° C. 35.3-Polymerization of ethylene 1 liter of reaction was heated under 80 ° C flowing nitrogen for 3 hours. The reactor was cooled to low At 30 ° C, add 500 ml of isobutane. Trimethylaluminum (3 ml of 2M in hexanes) is added to the reactor, then heated to 8 (rc. The reactor pressure is raised back to 13.8 bar 'and injected Ethylene obtained a total pressure of 23.8 bar. As described above 35.1, a supported catalyst (0.201 g of the supported catalyst solid in toluene slurry) was injected into the reactor under nitrogen to increase the reactor pressure to 25.4 bar. The catalyst activity was slightly over The high pressure keeps the ethylene intake air flow constant, thus allowing it to drop to 23.2 bar. The ethylene pressure in the reactor for most semi-polymerization reactions is estimated at 78 bar. The test was completed after 1.75 hours, and the polymer was washed with methanol / hydrochloric acid (2.5 liters / 50 ml), then with water / ethanol (4: 1 Wv), and at 40 ° C. (： The size of the vacuum paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm)-:-m *!-Ijl- m -I-—I- I (Please read the precautions on the back before filling this page)) Order 35 1238833 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (32) Dehydration. 166 grams of anhydrous polymer were recovered. Polymer analysis by GPC means that * Mw and Mη are 182000 and liooo, respectively. Example 36 ϋ · 1-2,6-Diethyl brewed vesicles 贰 (2,4,6-trimethyl 茇 彳 彳 & & chemical iron sheet in MAO / silicone by borrowing from the part prepared in Example 35.1 (about ^. 5 g) The supported catalyst was washed with 5 X 10 ml of toluene at IO ° C. The initial washing solution was a dark orange, and the subsequent washing was gradually faded until the final washing solution became clear. The solid was at l0. (rc vacuum dehydration to obtain a free-flowing solid supported catalyst. 36.2-Ethylene polymerization 1 liter reactor heated at 75 ° C for 1 hour under flowing nitrogen. Trimethyl | Lu (3 ml 2M in hexanes) Add to the reactor and then cool to 5 (rc. Isobutane (500 ml)) and add the temperature to 7fC. The reactor pressure rises to 13 bar. Allow ethylene to enter the reactor to obtain a total pressure of 21 bar (8 bar ethylene). The supported catalyst (0 ·; πg in toluene slurry) prepared as described in 26.1 above is injected into the reactor. Increase the pressure in consideration of the control of the reactor pressure The temperature rose to 80t: After 1 hour, another injection of the same catalyst (0.22 g in hexane slurry) was injected and the test was continued for 3.5 hours. 25 g of polymer was recovered. The polymer was analyzed by GPC to indicate Mw And Mη are 343000 and 35000, respectively. Example 37 Preparation of methyl aluminoxane from diethylpyridinium pyridine (2,4,6-trimethyl jasmonamine) digas main generation in ΜΑΟ / silica gas ( 24ml of 1.78M in toluene, supplied by Witco) was added to the silica (55g ES70X grade, supplied by Crosfield). It has been applied to China National Standards (CNS) (21GX297mm) on mobile nitrogen paper at 25 ° C. &Quot; " —J. -II ...............-I (Please read the notes on the back before filling this page) Order—II Booklet: | 36 1238833 A7 B7 Five 2. Description of the invention (33) Heating under gas; ε Xi oxygen / MAO is heated at 80 ° C for 1 hour, and then washed with methylben (5X10 ml whole). Half produced Silicone / mao slurry is cooled to the room (read the precautions on the back before filling this page), and is used for the next stage of catalyst preparation (the other half is set aside for Example 38). Diethylpyridine (2,4,6-trimethylaniline) digasified iron (73 mg) was dissolved in toluene and transferred to a half of silica / MAO / toluene, and allowed to react occasionally for 2 hours and mixed. The Shi Xi oxygen / MAO / Fe complex was washed with benzene (3 x 10 ml whole) at room temperature, and then the toluene was removed with hexane (2 x 10 ml whole) at room temperature, and finally at 80 ° C. Wash with hexane (3 x 10 ml whole). The resulting supported catalyst solid was dehydrated under vacuum at room temperature. 37.2- Polymerization of ethylene Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. A 1-liter reactor was heated at 80 ° C for 1 hour under flowing nitrogen. The reactor was cooled to below 30 ° C and 500 ml of isobutane was added. The reactor was heated to 77 ° C and the pressure increased to 13.8 bar. Ethylene was added to obtain a total pressure of 21.8 bar (8 bar ethylene). Triisobutylaluminum (5 ml of 1M in hexanes) was added to the reactor, and a supported catalyst (0.4 g in hexane slurry) prepared as above 37.1 after 20 minutes was injected into the reactor. And increase the pressure in the reactor pressure control during the test. The temperature rose to 80 ° C. The polymerization was terminated after 5 hours. 138 grams of polymer was recovered. Analysis of the polymer by GPC indicated that Mw and Mη were 567,000 and 53000, respectively. 37.3- Polymerization of ethylene A 1 liter reactor was heated at 78 ° C for 1 hour under flowing nitrogen. The reactor was cooled to below 30 ° C and 500 ml of isobutane was added. Triisobutylaluminum (3 ml of 1M in hexanes) was added to the reactor, and then heated to 78 ° C, and the pressure was raised. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 37 1238833 Central Ministry of Economic Affairs A7 printed by the Employees' Cooperatives of Lemon Provincial Bureau V. Invention Description (34) Up to 12.1 bar. Ethylene was added to obtain a total pressure of 32.0 bar (19.9 bar ethylene). The supported catalyst (0.0925 g, prepared as a slurry in hexane) was injected into the reactor as described above in 37.1, and the total pressure was controlled at 3 1.2 bar. The ethylene pressure during the polymerization was estimated to be about 19.1 bar. The polymerization was allowed to continue for 80 minutes. 181 g of polymer were recovered. The polymer was analyzed by GPC to indicate a polymerization of Mw and Mn of 595,000 and 44000 liters of 1L4-ethylene, respectively. A 1 liter reactor was heated under flowing nitrogen at 80 ° C for 1 hour, and then cooled to below 30 ° C. Triisobutylaluminum (3 ml of 1M in hexanes) was added to the reactor 'followed by 500 liters of isobutane. The reactor was heated to 78 = and the pressure increased to 13.5 bar. Ethylene was then added to obtain a total pressure of 17.6 bar (4 "bar ethylene). The supported catalyst (0.15 g, prepared in hexane as the loading solution) prepared in 37.1 above was injected into the reactor. The ethylene pressure during the polymerization was estimated to be about 47 bar. The polymerization was continued for 80 minutes. 21 grams of polymer were recovered. Polymers (31 > (: The analysis indicated that Mw and Mη were 347000 and 26000, respectively. Example 38 m2,6-diethylfluorenylpyridinium pyrene (2,6-diisopropylammonium amine) dioxide began to be removed in The second half of the silicon oxide / MAO prepared by Example 37 · 1 was dehydrated in vacuum. A whole portion of the dehydrated silicon oxide / MAO (1 g) was placed in a Chiron tube, 2,6- Diethylsulfanylpyridinium (2,6-diisopropylaniline) digassed cobalt (40 mg) was added as a dry powder. Then hexane (10 ml) was added to the Chiron tube, and Cobalt The mixture is mixed with silicon oxide / MAO / to form a slurry at room temperature for ^ hours. The mixture is dehydrated under vacuum at room temperature to leave a supported catalyst that is an anhydrous free-flowing powder. — (Read the precautions on the back before filling this page)

38 1238833 A7 B7 V. Description of the invention (35) 38.2-Polymerization of ethylene A 1-liter reactor was heated at 80 ° C under flowing nitrogen for 1 hour, and then cooled to 30 ° C. Hexane (250 ml), triisobutylaluminum (3 ml of 1 M in hexanes) and 250 ml of isobutane were added to the reactor. The reactor was heated to ⑼. ^ ;, and the pressure rose to 7.1 bar. Ethylene was added to obtain a total pressure of 19.2 bar (12.1 bar ethylene). The supported catalyst (0.245 g, prepared as a slurry in hexane) was injected into the reactor, and the reactor pressure was controlled during the test to increase the pressure. The polymerization was continued for 330 minutes and 3.3 grams of polymer was recovered. The polymer was analyzed by GPC to indicate Mw = 5300 and Mn = 1500.童 例 39- Polymerization of Ethanol in a Plasma Liquid Phase Using a Supported Catalyst Using Supported 2,6-Diethylpyridinylpyridine (2,4,6-trimethylaniline) Digas The catalyst was subjected to a series of polymerization tests. Example 39.1 A 1 liter reactor was heated at 80 ° C for 1 hour under flowing nitrogen and then cooled to 30 ° C. Isobutane (500 ml) was added to the reactor followed by triisobutylaluminum (3 ml of 11 ^ in hexanes). The reactor was heated to 78 ° C and the pressure was increased to 13.2 bar. The ethylene was added to obtain a total pressure of 26.2 bar. The catalyst of Example 37.1 (0.097 g 'was prepared as a slurry in hexane) was injected into the reactor. During the test, the reactor pressure was controlled at 26.0 bar (the ethylene pressure was estimated to be approximately 12 · 8 bar), and the temperature was adjusted to 80 ° C. The polymerization was allowed to continue for 60 minutes. 78 grams of polymer were recovered. GPC analysis of the polymer indicated that Mw and Mη were 528,000 and 40,000, respectively. Example 39.2 A 1 liter reactor was heated at 80 ° C for 1 hour under flowing nitrogen, and then cooled to 30 ° C. Isobutane (500ml), followed by triisobutylaluminum (3 亳 liter 丨 "Applicable to China Paper Standard (CNS) A4 specification (210 × 29? Mm) for this paper scale) -------- --r [- ---- II (Please read the notes on the back before filling this page}

1 1 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 39 1238833 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (36) Hexanes) was added to the reactor. The reactor was heated to 78 t and the pressure was increased to 13.4 bar. Ethylene was added to obtain a total pressure of 21.2 bar. The catalyst of Example 371 (0.124 g, slurried in hexane) was injected into the reactor. The ethylene pressure during the polymerization was estimated to be approximately 8.1 bar, and the temperature was adjusted to 80 ° C. The polymerization continued for 60 minutes. 47 grams of polymer were recovered. GPC analysis of the polymer indicated that Mw and Mη were 376,000 and 40,000, respectively. Example 39.3 A 1 liter reactor was heated at 80 ° C for 1 hour under flowing nitrogen and then cooled to 30 ° C. Triisobutylaluminum (3 ml of 1 M in hexanes) was added to the reactor, followed by 500 ml of isobutane. The reactor was heated to 781 and the pressure was increased to 13.0 bar. The ethylene was added to obtain a total pressure of 26.0 bar. The catalyst of Example 37.1 (0.0966 g, adjusted to a slurry in hexane and 0.25 l of N, N-dimethylaniline for 20 minutes) was injected into the reactor. Allowing the reactor pressure to drop to 22 5 bar reduces the catalyst activity. The ethylene pressure in the reactor during the majority of the polymerization was estimated to be 9.0 bar. The polymerization was allowed to continue for 60 minutes. 88 grams of polymer were recovered. The polymer analysis by gpc indicated that Mw and Mη were 430,000 and 35,000, respectively. Example 39.4 A 1 liter reactor was heated at 80 ° C for 1 hour under flowing nitrogen and then cooled to 30 ° C. Triisobutylaluminum (3 ml of 1 M in hexanes) was added to the reactor, followed by 500 ml of isobutane. The reactor was heated to 78 ° C and the pressure increased to 12.7 bar. Ethylene was added to obtain a total pressure of 14.7 bar. The catalyst of Example 37.1 (0.104 g, adjusted to a slurry in hexane) was injected into the reactor. The ethylene pressure during the polymerization was estimated to be 2.2 bar. The polymerization was allowed to continue for 60 minutes. 4.8 g of polymer was recovered. The polymer by GPC analysis indicates that Mw and Mη are 340,000 and this paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

I, ν " 40 1238833 A7 B7 Printed to the media by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (37) 36000 〇 Exemption 40-Use of a load-bearing contact in the plasma phase. A series of polymerization experiments were carried out on a supported catalyst of 2,6 · diethylpyridinidine (2,4,6 • trimethylbenzylamine) ferric chloride. Example 40.1 A 1 liter reactor was heated at 80 C under flowing nitrogen for 1 hour and then cooled to 30 C. Isobutane (500 ml), followed by triisobutylaluminum (3 ml 丨 "in hexanes) was added to the reactor. The reactor was heated until it was redundant, and the pressure was raised to 13.2 bar. Ethylene was added to obtain 26.2 Total bar pressure. The catalyst of Example 371 (0.097 g, adjusted to a slurry in hexane) was injected into the reactor. The reactor pressure was controlled at 26.0 bar (the ethylene pressure was estimated to be about 12.8 bar) during the test, and the temperature was adjusted to 80 ° C. Polymerization was continued for 60 minutes. 78 grams of polymer were recovered. The polymer was analyzed by GPC to indicate that Mw and Mn were 528000 and 40,000, respectively. Example 40.2 A 1-liter reactor was heated at 80 ° C under flowing nitrogen for 丨 hours and then cooled to 30 ° C. Isobutane (500 ml) followed by triisobutylaluminum (3 ml of 1M in hexanes) was added to the reactor. The reactor was heated to 78 ° C and the pressure increased by 13.4 bar. Ethylene was added to obtain 21.2 Total bar pressure. The touch of Example 37.1 (0.124 g 'adjusted into a polymer solution in the own courtyard) was injected into the reactor. The ethylene pressure during the polymerization reaction was estimated to be about 8.1 bar, and the temperature was adjusted to 80 ° C. The polymerization continued for 60 Minutes. 47 grams of polymer were recovered. Polymers were analyzed by GPC to indicate Mw and M They are 376000 and 40,000 respectively. Example 40.3 A 1-liter reactor was heated at 80 ° C under flowing nitrogen for 1 hour, and then cooled. This paper is scaled to the Chinese National Standard (CNS) A4 (210X297 mm) -V tmMmMmmt m ml In m ml —.1 (Please read the precautions on the back before filling this page) Order printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 1238833 A7 B7 V. Description of the invention (38) to 30 ° C. Triisobutyl aluminum ( 3 ml of 1M in hexanes) was added to the reactor, followed by 500 ml of isobutane. The reactor was heated to 78 ° C and the pressure was increased to 13.0 bar. Ethylene was added to obtain a total pressure of 26.0 bar. Touch of Example 37.1 Medium (0.0966 g, hexane and 0.25 liters of N, N-dimethylaniline adjusted to fill the liquid for 20 minutes) into the reactor. Any reactor pressure was reduced to 22.5 bar to reduce catalyst activity. During the semi-polymerization reaction The ethylene pressure in the reactor was estimated to be 9.0 bar. The polymerization was continued for 60 minutes. 88 grams of polymer were recovered. The polymer was analyzed by gpc to indicate that Mw and Mη were 430,000 and 35,000, respectively. Example 40.4 A 1 liter reactor was at 80 ° C at Heat under flowing nitrogen for 1 hour and then cool To 30 ° C. Triisobutylaluminum (3 ml of 1M in hexanes) was added to the reactor, followed by 500 ml of isobutane. The reactor was heated to 78 ° C and the pressure was raised to 12.7 bar. Adding Bake to obtain a total strength of 14.7 bar. Example 3 A catalyst of 7.1 (0.104 g, adjusted to a slurry in hexane) was injected into the reactor. The ethylene pressure during the polymerization was estimated to be 2.2 bar. The polymerization was allowed to continue for 60 minutes. 4.8 g of polymer was recovered. GPC analysis of the polymer indicated that Mw and Mη were 340,000 and 36,000, respectively. Example 41 This example shows the use of a combination of a metallocene catalyst with the iron complex-based catalyst of the present invention for polymerizing ethylene under slurry conditions. Example 41.1—Congratulations on metallocene-supported catalysts borrowed from silicon oxide (Crosfield grade ES70, previously added dissolved osmium (n-butylcyclopentadiene) to 20 (rc sintered under flowing nitrogen for 5 hours) Alkenyl) Zr (: i2 methyl aoxane (MAO) toluene solution. The dosage is 2.5 millimoles mao / gram — ^ m mu er.lv ml m n_i ml I (Please read the precautions on the back before (Fill in this page)

-42-Ϊ 238833 A7 B7 i. Description of the invention (39) Broken oxygen and 0.05 mol mole metal pentagram per gram of broken oxygen. The resulting slurry was gently searched for at least 1 hour and then dehydrated under reduced pressure to obtain a free-flowing powder. 11.2- Combine the metallocene / iron complex contact f with the supported metallocene catalyst (2.5 grams) prepared as described in step 41.1 above. Place it in the Schlenk tube and add 2 at ambient temperature. Slurry of 6-diethylfluorene-based cancer bite gas (2,4,6-trimethylaniline) digasified iron (73 mg) in hexane (10 ml). The mixture was heated to 80 ° C and left for 90 minutes, with occasional stirring to maintain a thorough mixed solution. The supernatant above the solid did not appear coloured. The resulting catalyst was vacuum dehydrated at 80 ° C to leave a dry, free-flowing powder. 41.3- Polymerization of ethylene A 1 liter reactor was heated at 80 ° C under flowing nitrogen for 1 hour and then cooled to 30 ° C. Triisobutylaluminum (3 ml of 1 M in hexanes) was added to the reactor, followed by 500 ml of isobutane. The reactor was heated to 77 ° C and the pressure increased to 12.9 bar. The ethylene was added to obtain a total pressure of 20.9 bar. The catalyst prepared as described in 41.2 above (0.100 g, slurried in hexane) was injected into the reactor. The ethylene pressure during the polymerization was estimated at 8 bar. The polymerization was allowed to continue for 60 minutes. 96 grams of polymer were recovered. The polymer by GPC analysis indicates that Mw and Mη are 471,000 and 30,000, respectively. ○ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) 41.4-Comparison Shows only using step 41.1 Supported metallocene catalyst polymerized ethylene. 1 liter reactor was heated at 80 ° C under flowing nitrogen for 1 hour, and then cooled to 30 ° C. Triisobutylaluminum (3 ml of 1M in hexanes) was added To the reactor, and then add 500 liters of isobutane. The reactor is heated to 75. (:, and the pressure is increased. The paper size applies the Chinese National Standard (CNS) A4 specification (21〇29 < 7 public envy) 43 1238833 Economy Printed by the Ministry of Standards and Standards Bureau Employees Cooperatives A7 B7 V. Description of the invention (40) to 12.7 bar. Add ethylene to obtain a total pressure of 20.7 bar. The supported metallocene catalyst (0.094 g, The hexane was adjusted to a slurry) and injected into the reactor. The ethylene pressure during the polymerization was estimated to be 8 bar. The polymerization was continued for 60 minutes. 49 grams of polymer were recovered. The polymer analysis by Gpc indicated that * Mw & Mn was 142000 and 53000, respectively. Example 42 -Gas phase polymerization It is shown that a combination of a metallocene-type catalyst and the iron complex-based catalyst of the present invention is used to polymerize acetic acid under gas-phase polymerization conditions. A 3-liter reactor is baked at 78 C under flowing nitrogen for at least 丨 hours, and then Cool to 30 ° C. Add powdered sodium gasification (300 g). The feed powder has an average particle diameter of less than 1 mm and has been dehydrated at 16 (TC vacuum pre-dehydration for more than 4 hours. Then add trimethylaluminum (3ml, 2M in hexanes, supplied by Yadeli.) Then the reactor was closed and heated to 78 ° C. Any alkylaluminum was purged of any poison present in the reactor for 90 minutes. Then the reactor was purged with nitrogen to 4 bar for 4 times and then vented. Hydrogen was added to the reactor to obtain a pressure of 0.08 bar, and then ethylene (8 bar) was added. The catalyst prepared in step 41.3 above (0.20 g) was Inject under nitrogen, and then adjust the temperature to 80 ° C. The polymerization was continued for 60 minutes, and then the nitrogen was purged from the reactor to stop the reaction and the temperature was lowered below 30 ° C. The polymer was washed with water to remove sodium chloride And then acidified methanol (50 Liters of hydrochloric acid / 2.5 liters of methanol), and finally washed with water / ethanol (4 · _1 v / v). The polymer was dehydrated under vacuum at 40 ° C for 16 hours. 64 g of anhydrous polymer was produced. The reaction product was subjected to Gpc ( Gel permeation chromatography). The obtained GPC curve has a unique dual mode, Mw = 253000 and polydispersity 64.9. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 1 ---.--- -衣-(Please read the precautions on the back before filling this page) Order 44 1238833 Μ ---------- ^ _ V. Description of the invention (Μ) and 2,6-diethylamine without ΤΙΒΑ This example shows that the polymerization of the vesicles (2, 6 and 1) is completely free of trialkyl isobutyl aluminum (TIB A) as the auxiliary catalyst, and it does not contain alkyl aluminum as a separate component as defined in the present invention (3). The compound has a positive effect on catalyst activity. The catalyst used was Example 37.i Preparer as above. The 厶 ΙΙΒΑ polymer 2.3-liter reactor was equipped with a stirrer and a jacket for temperature control at 11 () t: heated under anhydrous nitrogen for 1 hour. It was then cooled to 85 ° C, and triisobutylsulfonate was injected into an anhydrous hexane solution under nitrogen. The reactor was then fed with 1 liter of anhydrous isobutane. The stirred reactor contents were pressurized to 600 psig 'by maintaining the temperature at 85 ° C by adding anhydrous ethylene. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs = iv-.-· Ι: ·--1 ..... 1- is-I-—1 I (Please read the precautions on the back before filling this page ) The catalyst of Example 37.1 was injected into the reactor under nitrogen, and the injection line was purged with about 50 ml of isobutane. The reaction was then controlled to 600 psig by continuous addition of ethylene, and the conversion from ethylene consumption was monitored. The polymerization was carried out for the time specified in the table below. At this time, the addition of ethylene was stopped and the reactor was ventilated to atmospheric pressure, followed by polymer recovery and stabilization. The polymer was stabilized by adding dilute Irganox 1076 acetone solution to obtain 0.15% additive to the polymer. The reaction conditions, yield and activity are shown in the following table. Polymerization without TIBA (by comparison, the procedure of Example 43.1 was repeated without adding βα. The details are also shown in the following table '. It can be seen that the catalyst added with TIB Α can substantially improve the activity.

45 1238833 A7 B7 V. Description of the invention (42) Example catalyst weight (g) TIBA (1M) ml temperature ° c time minute yield gram productivity gram / gram active gram / gram / hour 43.1 0.1 3 80 35 530 5300 9085 43.2 0.103 0 80 55 495 4805 5242 Comparison of polymerization reaction with and without TIBA was also carried out on a pilot plant scale ^ 43.3-2,6-Diethylsulfanilidine (2,4,6-trimethylmosine) Preparation of ferrous nitride supported on 1VTAO / silicon oxide_ Unless otherwise specified, all operations are performed under nitrogen. Silox (256.62 g grade £ 870), (: 1 * 〇8 ^ 1 (1 supply) was calcined at 200 ° (: flowing nitrogen, and placed in a 2 liter round bottom bottle. Toluene (900 ml) was added to Siloxane, followed by addition of fluorenyl aluminoxane (441 ml '1.5M in toluene, supplied by Witco). Any MAO and siloxane reacted at room temperature for 10 minutes, at which time the temperature rose to 80 T :, and the slurry occasionally Shake the flask manually and mix. The temperature is maintained at 80-100 ° (: 2 hours. The 2,6-diethylpyridinium pyridine (2,4,6-trimethylaniline) dichloride prepared as in Example 9 above. Iron (3.48 g) was slurried in toluene (50 ml) and added to 80 ° C MAO / silica slurry. Another toluene (20 ml) was used to ensure that all iron complexes were moved to MAO / silica Oxygen. Then iron / MAO / silicone was heated at 80 ° C, occasionally shaken for 1.5 hours, and any solids were allowed to settle. The clear supernatant was decanted from the flask, and the catalyst was partially dehydrated at 80 ° C under vacuum for 30 minutes. Leave it at room temperature for 16 hours. Then dry the catalyst under vacuum at 80 ° C for another 5 hours to obtain anhydrous free-flowing powder, and no longer measure the solvent Scale applicable Chinese National Standard (CNS) A4 size (210 X 297 male directors)

LT -------- (Please read the notes on the back before filling out this page) Order Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 46 1238833

Fifth, the invention description (43) is out. Plant-scale polymerization (Apple 汸, 93 liter Phillips continuous polymerization loop reactor is used for polymerization. Ethylene, isobutane diluent, hydrogen, and the catalyst prepared in Example 1.3 above are metered into the reactor, while maintaining the reaction conditions as follows As shown in the table, the reactor is operated at a polyethylene flux of about 7.5 kg / hour. The molecular weight of the polymer is controlled by changing the rate of hydrogen addition. Two rounds are performed, and one round is not separately added as defined in the present invention as component (3). Compounds, and TiBA added in one round. Other conditions are the same except for the hydrogen addition rate, which decreases the hydrogen addition rate when adding ΉΒΑ and maintains similar HLMI. Test scale strains (please read the precautions on the back before filling in this Page) Ordered by the Central Bureau of Standards of the Ministry of Economic Affairs, printed by the Consumer Cooperative, and the reaction conditions do not include TIB A, added TIB A, temperature (° c) 90 90 pressure (psig) 600 600 yield (kg / hr) 7.4 7.3 ethylene (V%) 16.1 16.6 Isotin (L / H) 24 24 Hydrogen concentration (V%) 0.13 0.07 Dwell time (H) 1.6 1.6 ΤΙΒΑ (0 · 03M / L) (mL / H) 0 310 Catalyst productivity (g / g) 5310 7700 Blended product: HLMI (21.6 kg: g / 10 min) 4.7 4.0 Density (kg / m3) 959.9 959.4 This paper size applies to China National Standard (CNS) Α4 specification (210 × 297) 47 l238833 Printed on the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs shows that the addition of TIBA has a significant effect on productivity. Example 44-Slurry polymerization using various amounts of MAO and TMA This example shows the use of different amounts of methyl aluminum The effect of oxane (MAO) and trimethyl chain (TMA) on the activity. The TMA used is supplied by Yadeli. MAO is supplied by Yadeli as a 7 wt% solution, all volatiles are removed in vacuo and washed in hexane Residual solids were prepared three times, and then dehydrated once more in vacuum and stored under nitrogen. Diethylpyridinium pyrene (2,6_diisopropyl molybdenum) di_outer iron polymer ethylene is equipped with a mechanical stirrer and an internal cooling circuit. High pressure glass with internal pressure and temperature monitor is vacuum dehydrated at 50 ° C for 4 hours, often flushed with anhydrous nitrogen. 10 ml stainless steel injection tube at both ends is fed with 5 liters of toluene and 1 micromole under nitrogen. The ear was the iron catalyst prepared in Example 1. The second similar tube was fed with 5 ml of toluene, and the appropriate amount was filled with 0 and TAM (see the table below for the quantity). The toluene / ΜΑΟ / ΤΜΑ mixture was flowed with 200 ml of toluene The glass reactor was injected under a nitrogen pressure of 2 bar. The reactor was then vented, pressurized with 4 bar ethylene, and stirred at 1000 rpm at room temperature. After 15 minutes, the iron catalyst / toluene mixture was injected at 4 barene pressure. Inside the reactor, the reactor is ventilated to obtain a pressure differential. The temperature was maintained at 35-40. (: Record the temperature and ethylene flow rate every minute for 15 minutes. After 15 minutes, the reaction was quenched by injecting 10 ml of methanol. The reactor was ventilated, and another 200 ml of alcohol was added. The polymer was collected by filtration, and dehydrated in air. Overnight. The experiment was repeated several times with MA 〇 and TMA in varying amounts relative to the amount of iron complex (1 equivalent = 1 micromole). The following table shows the activity measured for each round. ---- (Please read the precautions on the back before filling out this page) Order -4-n In n I 1 mi li-· II I ..... 48 1238833 A7 V. Description of the invention (45) Each round measured TAM equivalent live weight (g / mmol · h.bar) MAO equivalent 200 500 1000 100 190 450 9400 500 8170 9750 9770 1000 12600 12410 13050 1000 equivalent MAO = 58 mg 1000 equivalent TMA = 0.10 ml 44.2-Polymerization of ethylene using 2,6-diethylfluorenylpyridinium (2,6-dimethylbenzylamine) iron dinitride to repeat ethylene experiment 44.1, but using the iron complex prepared as in Example 8 above. Results are shown in The following table: Activity measured for each round (g / mmol.h.bar) ΜΑΟquivalent 200 500 1000 100 708 270 4 4000 500 9600 13160 5920 1000 12480 14670 14160 (Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 1000 equivalents 1000 equivalents ΜΑΟ = 58 mg 1000 equivalents ΜΜ = 0.10 ml from the table above It can be seen that even when the total amount of aluminum in the system (derived from the combination of MAO and TMA) is equal, the activity will still vary depending on the source of aluminum. For example, using 1000 equivalents of TMA and 500 equivalents of MAO, observed activity ratios of 1000 equivalents of MAA and 500 equivalents of TMA Higher. This paper is sized for China National Standard (CNS) A4 (210X297mm) 49

Claims (1)

1238833 BS Co DS VI. Application for patents—Wai I 'No. 88 103771 Patent application for amendments to the scope of patent application This revision date · February 1994 L A catalyst for t-smoke, including (1) a formula B Compound K5 SB Consumption Cooperation among Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs 71 where M is Fe [II] or co; it is also a dentate, ammonium, nicotinic oxide, carboxylate, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, toluene An acid radical or trifluoro f-acid radical is an atom or group that can be co-bundled into a transition metal M; τ is the oxidation state of the transition metal 乂, and the valence m, r3, r4 of the 鸱 X atom or group, or R6 is selected from the group consisting of a substituted hydrocarbon group, a heteroalkyl group, or a substituted heteronictyl group; R5 or R7 is respectively selected from a substituted or unsubstituted cycloaliphatic group; and any two or more of them are a nicotyl group, When substituting a hydrocarbon group or a heteroalkyl group, these two or more may be linked to form-or multiple cyclic substituents; Alkane or mao) or modified methylaluminoxane (mma〇); and (3) except (2) 'a compound of formula 3, where each rule has a C ^ CI2 alkyl or halogen atom. … —R equipment ----- (please read the note on the back to write this page first) —order--f 50 CS388 1238833 Co D8 6. Application for patent scope 2. If the catalyst for item 1 of the patent scope is applied, Where R5 & R7 is selected from phenyl, 1-naphthyl, 2-naphthyl, 2-fluorenylphenyl, 2-ethylphenyl, 2,6-monoisopropylphenyl, 2,3-diphenyl Isopropylphenyl, 2,4-diisopropylphenyl, 2,6-mono-n-butylphenyl, 2,6-dimethylphenyl, 2,3-difluorenylphenyl, 2, 4-dimethylphenyl, 2-tert-butylphenyl, 2,6-diphenylphenyl, 2,4,6-difluorenylphenyl, 2,6-trifluoroJfluorenylphenyl , 4-bromo-2,6-difluorenylbenzyl, 3,5-digas-2,6-diethylphenyl, and 2,6-fluoren (2,6-dimethylbenzyl) phenyl , Cyclohexyl and ρ than bite. 3 · If the catalyst of item 1 of the patent application scope, in which the compound (丨) contains the skeletal unit of formula Z: (please read the note on the back of tf first? Matter v. ---- f write this page) Order '-Record the consumption cooperation of employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Du Yin S /, and M is Fe [II] or Co [II]; X-based halide, hydride, hydrocarbyl oxide, carboxylate, hydrocarbyl, substituted hydrocarbyl , Heterohydrocarbyl, tosylate or trifluoromethanesulfonate, are atoms or radicals that can be covalently or ionicly bonded to = metal M; τ is the oxidation state of the transition metal, and X is an atom or radical Valence; R1 to R4, "and Han ^ to Han28 are each selected from the group consisting of 氲 atom 'hydrocarbyl' substituted hydrocarbon group 'heteroalkyl or substituted heterocarbon di R] to R4, R6 and Rif any one or more of When a hydrocarbon group, a substituted hydrocarbon group, a heteroalkyl group, or a substituted heteroalkyl group, these two or more may be bonded to each other fe! Zij -Γγ ··-; 1- 'U :: NS) A · .;: ¾¾ (2.10 > : 297) 1238833 83 C3 D8 6. The scope of the patent application forms one or more cyclic substituents; it is stipulated that when the ring system p does not form a part of the polyaromatic ring system, at least one of r19, r21, r21, and R22 It is a hydrocarbon group, a substituted hydrocarbon group, a heteroalkyl group, or a substituted heteroalkyl group. ^ Declared the catalyst of item 5 of patent dry 11, in which the ring system p and Q of formula Z are 2,6 · nicotylphenyl or fused ring polyaromatic compound, respectively. 5. The catalyst according to item 4 of the application, wherein the ring systems P and Q of formula Z are 1-naphthyl, 2-naphthyl, buffyl or 8-σquinolinyl. 6. If the catalytic compound in the old or the third item of the patent application is applied, the hearts 4㈣ to ρ are selected from the group consisting of gas and ία hydrocarbon group, respectively. 7. The catalyst as claimed in item 6 of the patent claim, wherein R1 to R4, R6 and R! 9SR28 in the compounds of formula B and Z are selected from methyl, ethyl, n-propyl, n-butyl, n-hexyl and Is octyl. Green 8. The catalyst according to item 1 of the scope of patent application, wherein the compound (1) comprises a skeleton unit of formula T: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, where M is Fe [II] or Co [II]; X is a halide, hydride, hydrocarbyl oxide, acid salt, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, Ben Shihuang 52 1238833 Co D3 Consumption cooperation by employees of the Intellectual Property Bureau of the Ministry of Economics, loosely printed VI. Application for patents in acidic or tri-methyl acetate, which can be covalently or ionically bonded to the atoms of the transition metal M or T is the oxidation state of transition metal M, μ is the valence of X atom or group; R 丨 to R4, ... and ^^ to 32 are respectively selected from hydrogen, _ atom, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl or substituted Heterohydrocarbon beauty · When R1 to any of ⑻ ^: one or more is a hydrocarbon group, a substituted hydrocarbon group, a heteroalkyl group or a substituted heteroalkyl group, these two or more may be bonded to form one or more rings Substituents. 9. The catalyst according to item 丨, 3, or 8 of the scope of patent application, wherein the x atom or group in the compounds of formula B, Z and T is chloride, bromide, methoxide, ethoxide, isopropyl Oxides, phenoxides, formate, acetate, benzate, methyl, ethyl, propyl, butyl, octyl: decyl, phenyl or benzyl. 10. The catalyst according to item 1 of the scope of patent application, wherein the compound (1) contains 2.6-diethylpyridinium (2 heptadiisopropylaniline) with ^ 2, 2.6-diethylpyridinyl (2, 6-diisopropylaniline) MnCl2, 2.6-diethylpyridine (2,6-diisopropylaniline) coCl2, 2.6-diethylpyridinepyridine (2-third butylaniline) FeCl2 , 2.6-—Ethylpyridinium (2,3-dimethylaniline) FeCi2, 2.6-Diethylpyridinium (2-methylaniline) FeCl2, 2.6-Diethylpyridinium (2) , 4-Difluorenylaniline) FeCl2, 2.6-diethylfluorenylpyridine (2,6_difluorenylaniline) FeCl2, 2.6-diethylfluorinylpyridinium (254,6-trifluorenylaniline) FeCl2 2.6- dialdehyde imine pyridine hydrazone (2,6-difluorenylbenzylamine) FeCl2, 2.6- dialdehyde imine pyridine hydrazone (2,6-diethylbenzylamine) Feci2, (¾ Read the note on the back first ? --- scold this page) Order. Green · (210 >: 297 53 1238833 Bo Co D8 肀 Please request the employees of the Intellectual Property Bureau of the Ministry of Economic Affairs to eliminate the yellow cooperatives 'seal-;!,'] 《2.6-Dialdehyde Aminopyridine (2,6-diisopropylaniline) FeCl2, 2.6-diacid Iminepyridine fluorene (1-naphthylamino) FeCl2 or 2,6 · 贰 (丨, diphenylhydrazone) pyridine FeCl2. 11. The catalyst according to item 丨 of the patent application range, wherein the compound (3) comprises- Methyl I (TMA), trimethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octyl aluminum, ethyl aluminum dichloride or diethyl aluminum chloride. 12 · If applying for a patent The catalyst of the range item 1, wherein the ratio of the compound (3) to the compound (2) is greater than 1: 1. U. The catalyst of the range of item 12 of the patent application, wherein the ratio of the compound (3) to the compound (2) is greater than 5 : 1. 14. If the catalyst according to item 13 of the patent application, wherein the ratio of compound (3) to compound (2) is greater than i0: i. 15 · If the catalyst according to item 1 of the patent application, it is supported on _ On a supporting material or a polymer or prepolymer. 16. For example, the catalyst in the scope of patent application No. 15, wherein the supporting material is Shi Xi oxygen, aluminous oxygen or cross-oxygen and the polymer or prepolymer system Polyethylene, polystyrene, or poly (amino styrene). 17. The catalyst according to item 15 of the patent application, wherein the monomer is silicon oxide and is compounded. The compound (2) is methyl sulphurate, and the compound (3) is trimethylpyridine) or triisobutylaluminum (TIBA). 18. If the catalyst in item 1 of the patent application scope is applied, it further includes human Louis test. 19. The catalyst as claimed in claim 18, further comprising a diamine or an aromatic compound. Seed Species (please read the note on the back of this page first)-Binding J Zhang Zhang Xiao Xiao Shen Shou Jia: ΐΐψ (CNS) G Specification (210 >: 297 BS C8 Patent Application Range ~ Kind of Polymerization and A method for copolymerizing 1-olefins to obtain a man's cheek, which comprises contacting the monomeric olefin with a polymerization catalyst as defined in the first item of the patent under the conditions of 5: = the compound is activated by a silk weaver The contact conditions are 2 "5 early body 'and the polymerization conditions are solution phase, slurry liquid phase or gas phase. For example, the method of item 20 of the patent scope, wherein the polymerization is to destroy the liquid phase in an autoclave or a continuous circuit. The reaction is carried out in a reactor. 22. The method of claim 20 in the patent application, wherein the polymerization is carried out in a polymer liquid phase, and the compound (3) is triisobutylaluminum (TIBA) or trimethylammonium (butylene). ] ViA) 〇23. The method according to item 20 of the patent application, wherein the polymerization is performed under a gas-phase fluidized bed condition. 24. The method according to item 20 of the patent application, wherein the polymerization is performed at At a pressure of 100 bar, and at a temperature of 50 to 12 ° C. 25. Such as the scope of patent application No. 20 Method, wherein the polymerization is carried out in the gas phase, and the compound (3) is trimethyl aluminum (TMA). 26 · —a compound of formula B for improving the 1st olefin as described in the scope of the patent application, for the polymerization of 1-olefins A method of catalyst activity at the time, the method includes using a compound of the formula AIR3, where each R is Ci-C] 2 alkyl or halogen atom Installation · (Read the notes on the back page and write this page) Order. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ¾ i 55